Table iii



United States Patent 26,565 2-0RTHO-HYDROXY-PHENYL-4-(3H)-QUINAZOLINONES John Leo Rodgers, Somerville, and Jerry Peter Milionis,Franklin Township, Somerset County, NJ assignors to American CynamidCompany, Stamford, Conn., a corporation of Maine No Drawing. OriginalNo. 3,169,129, dated Feb. 9, 1965,

Ser. No. 279,631, May 10, 1963. Application for reissue Mar. 2, 1966,Ser. No. 536,533

Int. Cl. C07d 51/48; F2lv 9/02 U.S. Cl. 260251 9 Claims Matter enclosedin heavy brackets appears in the original patent but forms no part ofthis reissue specification; matter printed in italics indicates theadditions made by reissue.

wherein R R R and R each represent hydrogen or a substituent such ashalogen, hydroxyl, an alkyl or alkoxy of 14 carbons; and R representshydrogen or an alkyl of 1-4 carbons. Within this group of compounds, apreferred subclass is that in which R is hydroxyl and the other Rs" areas defined above. Accordingly, they are used herein for the purposes ofprimary illustration.

Fluorescence, or the emission by certain materials (phosphors) of lightenergy (luminescence) of one wavelength when irradiated by excitinglight of a different wavelength, usually lower, has been well-known formany years. Also well-known is the phenomenon of phosphorescenceexhibited by some materials, i.e., persistence of the luminescence afterremoval of the source of exciting radiation. In the past, variouspractical applications of fluorescent phenomena have been proposed withvarying degrees of success.

Usually these involved irradiation with ultraviolet light, resulting inillumination by emission of visible light at longer wavelengths. Forsuch purposes, inorganic phosphors have had quite wide application. Ingeneral, however, organic materials have been found applicable only invery few instances, being limited, in part, by a lower degree ofstability than inorganic materials under the types of irradiationencountered. Moreover, most of the applicable compounds have been dyessuch as rhodamine, which are self-colored. This is definitelyundesirable for many potential applications.

Fluorescence is also involved in the field of brighteners or opticalbleaches. Here, organic materials have been applied with great successon a broad commercial scale. However, organic materials found useful forsuch purposes have not been found generally useful for fluorescentilluminating purposes. In large part this is due to minimal fluorescenceof the material in the solid state and to relative instability anddecided degradation under continued exposure to exciting radiation inthe ultraviolet range.

Reissued Apr. 29, 1969 In the illuminating field, as noted above, somelimited use of organic materials as fluorescers has been proposed. Onesuch is in application as screens, not as a major source of illuminationbut for purposes of shading or modifying the color or tone of light fromsome other source. Such a screen may be used to improve the spectra oflight sources deficient in one or more spectral color elements to a moredesirable spectrum or shade of light.

One example of such application is found in U.S. Patent No. 1,150,118.Therein, a fluorescent screen or surface using an organic material suchas a rhodamine dye is used to impart an improved color value toillumination emitted from a mercury vapor lamp, i.e., to produce awhiter light closer to daylight than is the greenish-blue tone of lightnormally produced by a mercury vapor lamp. Thus, such a lighttransforming screen or reflector is useful for converting some of therays of the light source to light of a more desirable wavelength. Suchsources could be mercury vapor lamps or tungsten or carbon filamentlamps. Other illustrations are found for example in U.S. Patents Nos.2,177,701 and 2,149,992. Fluorescence phenomena have also been appliedto coating compositions, for example, in uses involving pigmentcompositions.

However, one of the principal deterents to wider use of organicmaterials in fluorescent screens or films still remains the relativeinstability encountered on prolonged exposure to exciting ultravioletlight and/or the relatively weak fluorescence in the solid state. Thus,for example, many of the compounds useful as brighteners or opticalbleaches do show the desired shades of fluorescence but lack sufficientstability against deterioration when exposed to ultraviolet excitinglight for extended periods. More over, many fluoresce only weakly orimperceptibly in the solid state.

Consequently, in illumination, and in related arts, there remains adefinite need for suitable fluorescent low-cost, organic materials. Suchmaterials should exhibit little or no visible color in white light.Under ultraviolet irradiation in the solid state they should fluorescestrongly in desirable shades. They should be adequately stable to theeffect of such irradiation as well as to the effect of heat for extendedperiods.

Such materials would be extremely useful for a variety of applications,especially in the illumination field or in other fields wherefluorescence is desirable. Thus, in the illumination field, screens orpanels giving various shades of light under excitation would be useful,not only for general illumination but to produce novel or theatricaleffects, signs, coating compositions, fluorescent finishes, fluorescentlamps and the like.

It is, therefore, the principal object of the present invention toprovide such organic materials. In the present invention this object hasbeen accomplished to a surprisingly successful degree by the discoveryand use of the compounds of Formulae I which were discussed above. Inaccordance with the present invention, it has been found that colorlessor nearly colorless compounds so defined show strong fluorescence in thesolid state, give off desirable shades of visible light when irradiatedwith ultraviolet light; have a high degree of stability to the effect ofheat; and do not excessively deteriorate or lose fluorescence duringexposure to ultraviolet light, even over prolonged periods.

Accordingly, these compounds are highly useful in applications requiringemission of visible light on exposure to ultraviolet light. They may beformulated successfully in solid form in screens, films, coatings, andthe like to obtain the fluorescent effects desired. Discovery of thefluorescent properties and stability of these compounds in the solidstate and their applicability for fluorescent purposes was completelyunpredictable and unexpected.

ice

ll P2 NHC lizNCOOCgIIg,

YQ l NH Although yields by this method generally are not as high asmight be desired, this method often is convenient. It affords aprocedure for obtaining various substituted derivatives from morereadily available or more easily prepared starting materials. Thus, bychoosing appropriately substituted anilides, the desired substitutedquinazolones may be prepared. Illustrative aroyl anilides which may beused in this method include:

p-Anisanilide 4'-butyl-p-tanisanilide 4'-chloro-p-anisanilide4'-bromo-p-anisanilide 4'-bromo-p-anisanilide Benzanilide4'-methylbenzanilide 4'-chlorobenzanilide 2-chlorobenzanilidep-Benzanisidide p-Anis-o-anisidide p-Anis-p-anisidide4,4-dichlorobenzanilide 2,4-dichlorobenzanilide2-methyl-4'-chlorobenzanilide 2-methyl-4'-butylbenzanilide Method(B).Reaction of an anthranilamide with an aromatic aldehyde by heatingin the presence of a solvent, such as ethanol, to give an anil typewhich then is ring closed to a dihydroquinazolone in the presence ofcaustic; the dihydroquinazolone then being oxidized to the correspondingquinazolone. This may be illustrated by the following reaction scheme:

This procedue also may be used to obtain substituted derivatives byusing appropriately substituted starting materials. Illustrativeanthranilamides, for example, include those having chloroorbromo-substituents in the 4- or the 5-position. Illustrative aldehydesinclude, for example:

Benzaldehyde 2,4-dimethoxybenzaldehyde o-Anisaldehyde2-chlorobenzaldehyde p-Anisaldehyde 4-chlorobenzaldehyde m-Anisaldehyde4-bromobenzaldehyde Method (C).--By cyclization of N-aroylanthranilamides under alkaline conditions as illustrated in thefollowing reaction scheme.

N NIICOAr DIP I TA:

CONIIz Qt Here again substituted derivatives may be prepared by havingappropriate substituents in the starting materials.

Various known methods are available for evaluation of these compounds asorganic fluorescent materials; for example determination of the colorand strength of fiuorescence; the stability on irradiation; and thelike. Stability, however, may vary appreciably, depending on the testconditions. For example, in solution some compounds may be relativelyunstable yet in the solid state show extremely high stability. Thus, forexample, when certain compounds are incorporated in cellulose acetateand exposed to UV light in a Fade-Ometer" they may show stability ofseemingly low order. However, the same compound in the solid state, asin the form of a thin film deposited from solution, in many instancesshows a very high degree of stability.

Diflerent compounds of the present invention when exposed to UV lightshow fluorescence in various colors. As stated above, they may showvarying degrees of stability. Also as noted above, preferred compoundsof the invention, especially as to stability and as to intensity andshade of emitted visible light when exposed to UV are those of Formula Iin which R is an ortho-hydroxy substituent. Among these,2-(2-hydroxyphenyl)-4(3)-quinazolone is especially desirable because ofits shade of fluorescent light and high stability.

Compounds of the invention may be used in a very large variety ofapplications, based on their fluorescence and stability properties.Thus, for example, they may be used in lighting panels; in various typesof plastic compositions; in inks, paints and the like; or in anyapplication applied to a surface or in a film for emission of visiblelight upon exposure to UV light. A specific application of interest isthe use of a fluorescent compound of the invention in printing inks,paints, enamels and other surface coating compositions to produce acomposition which has one appearance by daylight and a completelydifferent appearance or color under UV or black light. Such eflects areuseful for various decorative uses and for purposes of identification orsecurity.

As fiuorescers, compounds, of the invention absorb UV light and byvirtue of this property also have some application as protective agentsin plastic compositions, that is as UV absorbers. In such cases, it isthe UV-absorbing property which is important rather than conversion ofincident UV light to emitted visible light.

This invention will be further illustrated in conjunction with thefollowing examples. Therein, unless otherwise noted, all parts andpercentages are by weight and temperatures are in degrees centigrade.Preparation of the 4(3)-quinazolones is illustrated by Examples 1-37inclusive. Preparation of the preferred2-(2-hydroxylphenyl)-4(3)quinazolones which are believed to be newcompounds is illustrated in Examples 2237. Properties and uses of thesecompounds are shown in the remaining examples,

EXAMPLE 1 Preparation of 2-(4-methoxyphenyl)-4(3)-quinazolone Asillustrative of the procedure of Method (A): a mixture of 22.7 g. ofp-anisanilide, 8.9 g. of urethane, 112 g.

of P in 250 g. of toluene is refluxed with vigorous stirring for 3hours. The toluene is decanted and the remaining solid is added tocrushed ice. The suspension is treated with aqueous sodium hydroxide toneutralize and the crude product collected. This is recrystallized fromethanol; M.P. 245-246.5 C.

EXAMPLES 2-15 The procedure of Method (A) as shown in Example 1 isrepeated, substituting for the p-anisanilide equimolar amounts ofvarious anilides and anisidides. Starting ma- 1 terials and resultant-4(3)-quinazolones are shown in the following table.

9. 3-chlorobenzanilide.. 2(3-chlorophenyl]- 4-ethylbenzanilldo.2-(4-ethylphenyb- 13. 4-bromo-3-chlorobenzanillde6-bromo-2-(3rch1or0phenyl- 14 2'-propoxy-3,5-dibromo-8-pr0poxy-2-(3,5-dibromo banzanilide. phenyl)- 154'-ethyl-4-hydroxybenzanilide. (yethyl-2-(4hydroxyphenyl)- EXAMPLE l62-phenyl-4 3 )-quinazolone As illustrative of Method (B), a solutioncontaining 204 g. of anthranilamide and 2 ml. of cone. l-iCl in 800 ml.of ethanol is treated with 160 g. of benzaldehyde followed by heatingfor minutes. Ten percent aqueous sodium hydroxide (2.7 liters) is thenadded and the mixture is heated to distil oif the ethanol. The crudeproduct is collected by filtration and recrystallized from ethanol; M.P.23423S C. The resultant dihydro compound (100 g.) is slurried in 2.5liters of 2.5% aqueous caustic and heated to C. Sodium hypochlorite (450ml. 10% solution) is gradually added while heating to C. in one hour.The reaction mixture is clarified hot, cooled and acidified with aceticacid. The product is collected, washed r a with water and dried; MP.240-241 C.

TABLE II Ex. No. Starting Material -4(3)-qulnazolone 1T o-Anisaldehydo2-(2-methoxyphenyl)- 18 p'lolualdehyde 2-(4-methylghenyb- 202.4-(lichlorobenzaldehyde 2-(2,4-dich orophenyl)- 214-cthoxy3-Inethoxybenzalde- 2-(4-ethoxy-3-methoxyhyde. phenyll- In thefollowing examples preparation and utilization of the preferred subclassof compounds of Formula I are illustrated. As there noted, thesecompounds are within Formula Ibut have the structure R R R and R are asdefined above for Formula I. In most cases R and R will be hydrogen.

EXAMPLE 22 2- Z-hydroxyphenyl -4( 3 )-quinazolone A mixture of 648. g.salicyclic acid, 580 g. thionyl chloride, and 3 ml. of pyridine isheated four hours at 40 C. The excess SOCl is removed by vacuumdistillation. This as is" acid chloride is added dropwise to a stirredrefluxing mixture of 500 g. anthranilamide, 635 g. of K CO and 5.5liters of dry ether. After refluxing 3 hours the ether is removed bydistillation and the product washed with water. This is slurried in 14liters of 5% NaOH and boiled for one hour. After cooling the solutionwas neutralized with acetic acid and the product was isolated byfiltration; 634 g., M.P. 280-284 C. This is recrystallized from aceticacid to give a light yellow solid, M.P. 297-298 C.

EXAMPLE 23 The procedure of Example 22 is employed, substituting4-ethoxysalicyclic acid in place of salicyclic acid, to synthesize2-(4-ethoxy-2-hydroxyphenyl) 4(3)-quinazolone.

EXAMPLE 24 2- (4-chloro-2-hydroxyphenyl -4 (3 )-quinazolone NH H4-chlorosalicyclic acid (86.3 g., 0.5 m.), thionyl chloride (150 cc.)and pyridine (0.5 cc.) are stirred for 3 hours at 30-40 C. Excess SOClis removed by vacuum distillation below 40 C. The resulting acidchloride is added over a period of one-half hour to a mixture of 55 g.of anthranilamide and 70 g. of anhydrous potassium carbonate in 200 cc.of benzene and 450 g. of diethyl ether. The mixture is stirred overnightand then treated with 1400 cc. of 5% aqueous sodium hydroxide. Thereaction mixture is heated to C. for one hour, cooled and neutralizedwith acetic acid. The product is collected by filtration andrecrystallized from phenol. It shows a melting point of 3457 C.

point of 253-5 C.

EXAMPLE 26 2- 3,S-dichloro-2-hydroxyphenyl -4(3 -quinazolone One-halfmol (103.5 g.) of 3,5-dichlorosalicylic acid is used in place of the4-chlorosalicylic acid in Example 24. The desired product is purifiedfrom methyl Cellosolve.

EXAMPLE 27 One-half mol (148 g.) of 3,5-dibromo salicylic acid isemployed in place of the 4-chlorosalicylic acid in Example 24. Theproduct, 2-(3,5-dibromo-2-hydroxyphenyl)-4(3)-quinazolone isrecrystallized from pyridine.

EXAMPLE 28 Eighty-six parts of 5 chlorosalicylic acid is used in placeof the 4 chlorosalicylic acid in Example 24. The desired product, 2 (5chloro 2 hydroxyphenyl)-4 7 (3) quinazolone is isolated andrecrystallized from dimethylformamide.

EXAMPLES 29-33 Using the general procedure of Example 24, butsubstituting the appropriate starting acid, the compounds shown in thefollowing Table III are prepared.

TABLE III Ex. No.: -4( 3 )-quinazolone 29 2(2,4-dihydroxyphenyl)- 302(2-hydroxy-4-butoxyphenyl)- 31 2(2-hydroxy-5-butylphenyl)- 322(2-hydroxy-5-iodophenyl)- 33 2(2-hydroxy-4-methoxyphenyl)- It is alsowithin the scope of the present invention to convert the 2-hydroxyphenylcompounds into other derivatives by further reaction of the hydroxy]group. This is shown in the following examples.

EXAMPLE 34 2- (Z-carbethoxyoxyphenyl -4( 3 -quinazolone 2 (2hydroxyphenyl) 4(3) quinazolone (71.5 g., 0.3 m.) and sodium hydroxide(13.2 g., 0.3 m.) in 1000 cc. of water is treated with 38.5 g. (0.33 m.)of ethyl chlorocarbonate. The reaction is complete after one-half hourand the product is collected by filtration. The prodduct isrecrystallized several times from a 3:1 mixture of toluene andmethylcyclohexane, M.P. 145-6 C.

EXAMPLE 35 (l) 2-(Z-hydroxyphenyl)-3-methyl-4(3 -quinazolone (2)2-(2-methoxyphenyl -3-methyl-4(3 )-quinazolone EXAMPLE 36 A mixture of 2(2 hydroxyphenyl) 4(3) quinazolone 11.9 g. (.05 m.) and 7.6 g. (.06 m.)of butyl bromide in 200 ml. of acetone containing 7.9 g. (.05 m.) ofanhydrous potassium carbonate is refluxed for 12 hours. The reactionmixture is then added to water and the solid product collected. Thesolid is extracted with alcoholic aqueous sodium hydroxide and theextract is neutralized with dilute hydrochloric acid. The product, 3butyl 2 (2 hydroxy phenyl) 4(3) quinazolone, is collected and purified.

EXAMPLE 37 The above procedure is used to prepare: 3 ethyl 2- (2 hydroxy3,5 dichlorophenyl) 4(3) quinazolone from ethyl iodide and 2 (2 hydroxy3,5 dichlorophenyl) 4( 3) quinazolone and to prepare a 3 propyl- 2 (2hydroxy 3 methylphenyl) 4(3) quinazolone from 2 (2 hydroxy 3methylphenyl) 4(3) quinazolone and propyl bromide.

As noted above, in the solid state, compounds of this invention exhibita wide range of fluorescent color. Typical illustrations of fluorescentcolor when exposed to UV radiation (3650 A.) in the solid state areshown in the following table.

2-(4-methoxyphenyl)-6-buty1 Blue white. 2-(4-methoxyphenyl)-6- methoxyDo. 2-(4-methoxyphenyl)-8- methoxy Do. 2-(2-methoxyphenyl)Lightyellowish green.

2-(4-ethoxy-3-methoxyphenyl) White. 2-(2-methoxyphenyl)-3-methyl Lightviolet.

2-(2-hydroxyphenyl) Green. 2-(2-hydroxy-4-ethoxyphenyl) Bluish white.2-( 2-hydroxy-4-chlorophenyl Green. 2-(2-hydroxy-3-methylphenyl) Yellowgreen.

2-(2-hydroxy-3,5-dichlorophenyl Yellow. 2-(2-hydroxy-5-chlor0phenyl)Yellow green. 2-(2-hydr0xyphenyl)-3-methyl Green.

The 2 (2 hydroxyaryl) 4(3) quinazolones had intensities of fluorescencevastly superior to the derivatives not possessing 2-hydroxyarylstructures.

EXAMPLE 38 Illustrative 4(3 )-quinazolones were examined in sodiumchloride wafers to determine the intensity of luminescence and lightstability as shown by the percent luminescence remaining after prolongedexposure to UV light. Wafers containing 0.2% luminescer are prepared bygrinding the luminescer with the NaCl in a porcelain mortar until a finepowder having uniform luminescence under a black light is obtained. Oneor two grams of this powdered mixture is sintered in a 1.750-inchdiameter die, at a pressure of 150,000 lb./in. to form a transparent totranslucent wafer. The wafer is then mounted on a 2 x 2 inch opticalglass slide with black, pressure-sensitive plastic tape. Observationsare made on the color 01 luminescence under black light. The intensityof fluorescence of each wafer is determined using a Galvanek-Morrisonfluorimeter. Fluorescence is compared to a blue fiuorescing plasticsheet which is used as a standard for comparative purposes and isarbitrarily assigned the fluorescent strength of 1.0. In order to allowthe intensity of luminescence to stabilize, the first hours of exposureare considered as a break-in period. The wafers are aged in afluorescent sun lamp black light exposure unit (FSBL) and the change offluorescent intensity with time of exposure is determined. In thefollowing Table IV, illustrative results obtained with one gram waferscontaining various quinazolones after 3380 hours exposure are given.Results obtained with 4(3)-quinazolones that do not have the 2-hydroxysubstituent are first shown; followed by those for the new 2-hydroxycompounds of the present invention.

TAB LE IV Percent Lumines- Itolntlvo ccnco Color of Initial After4(3)-quinazolone Luminescence Intensity E xposure 2-(4-methoxyphany0-Blue 0. 24 24 2-phenyl- Dull blue 0.10 27 6-methoxy-2-phenyl- .do. 0. 0528 2- (.Z-hyd r0xy-4-ethoxyphen yl)- A qua 0. B4 652-(Z-hydroxyphenylJ-flil} Green. I). 86 73 quinazolone.

In the following Table V typical results obtained using two gram wafersexposed for 3100 hours are shown.

In the following Table VI illustrative results on two gram wafers after4700 hours exposure are shown.

dure, i.e., by milling into samples of the same commercial ink vehiclepigmented with the following commercial pigments: (A) Litho Red; (B)Chrome Green; and (C) Iron Blue respectively. Illustrative results areshown below in Table VIII.

TABLE VIII Parts per Hundred oi- Compound Color (percent Pigment Vehicleadded) Daylight Black Light None Red Red. (AL-m 15 l N to .1 glellow onenck. 50 l 0 Green c 33.3 ee.e{ g 2512i EXAMPLE 40 Samples of molybdateorange and chrome green type TABLE T" rotogravure inks containing 5% ofthe compounds LPercent of Example 22 and of Example 23 were prepared byshot mmive 1.2 21: milling the additives into the wet inks using atwo-roll 4 i I guitar st I Init i al F Aft r blending machine. Ablending time of 24 hours was "meme msum allowed. Drawdowns were madeand examined under vis- 2-(2-hydroxyphenyl) Gr n .9 71 ible and black liht. bs rvati r r o 244-methoxyphenyl) Dull White... 0.33 23 25 g 0 e onsa e as ec rded In Table IX.

TABLE IX Additive Black Light Ink Paper Stock Color Percent Ex. No.Fluorescence Color Visual Color 0 None Reddish-orange. Roto-orange Greentint 5 22 Yellow Do. 5 23 Dullgreen Do. 0 Very dull red. Rcddish-orange.Do White bond (hrightened). 5 22 Ten Do. 5 23 Brown Do. 0 Very dullgreenl Green. Rota-green..- Green tint 5 22 Bright green.. Do. 5 23Bluish-green Do. 0 Very dull greenish-gray--. Green. Do White bond(brighteued) 5 22 Green Do. 5 23 Bluish-green Do.

As can be seen from Tables IV, V and VI, the intensity of luminescenceand light stability of the 2-(2-hydroxyaryl)-quinazolones are markedlysuperior.

EXAMPLE 39 The Z-hydroxyphenyl derivative of Example 22 was evaluated asthe fiuorescer in (i) a colorless unpigmented ink composition; and (2)in colored pigmented ink compositions. The resultant coatings have oneappearance by daylight and a different appearance or color of strongintensity under UV light. Preparations of the inks and illustrativeresults are shown as follows:

(1) Unpigmented ink Colorless inks, luminescent green under ultravioletlight, were prepared by milling differing amounts of the compound ofExample 22 into a commercial ink vehicle ([PI K-592 Vaposet). Drawdownswere made from this ink and samples were subjected to black lightexposure. The intensity of fluorescence of each drawdown was determined(by the procedure of Example 37) and the hours of exposure necessary todecrease the luminescence to a relative intensity of 0.01 were thendetermined. Illustrative results are shown in Table VII below.

TABLE VII Relative Percent Initial Hours Cone. Intensity Exposure (2)Pigmented inks The compound was incorporated by the same proce- Twosamples of fluorescent type T rotogravure ink were prepared by shotmilling the following formulations on a 2-roll blender for 24 hours.

Formulation A: Parts Type T Vehicle 70 Chrome Green 15 Luminescer (Ex.13) 15 Formulation B:

Type T" Vehicle 60 Molybdate Orange 20 Luminescer (Ex. 13) 20 A drawdownof Formula A roto ink exhibited a strong green fluorescence while adrawdown of Formula B exhibited a strong yellow fluorescence under theblack light.

EXAMPLE 41 Samples of letterpress black ink were similarly prepared withcompounds of Examples 16, 18 and 19. The drawdowns exhibit strong yellowgreen, yellow and yellow green luminescence respectively, under blacklight.

EXAMPLE 42 Two and one-half grams of compound of Example 22 isthoroughly mixed into 7.5 g. of a white-paint having the followingformulation:

Percent Titanium dioxide 11.0 Titanium calcium 30.0 Zinc oxide 2.4Linseed soya-alkyd resin 23.9 Mineral spirits 30.4 Driers 2.3

A drawdown is prepared which has intense green fluorescence under blacklight.

EXAMPLE 43 Seven and one-half grams of a varnish consisting of 50%linseed soya ester gum alkyd resin in 50% petroleum thinner and driersis treated with 2.5 g. of compound of Example 22. A drawdown is preparedwhich is essentially colorless and which luminesces bright green underblack light.

EXAMPLE 44 To 7.5 g. of a pastel green paint having the followingformulation:

Percent Titanium dioxide 17 Magnesium sulfate 14 Barium sulfate 8 Greentinting color 1 Polyvinylacetate copolymer 12 Water 48 is added 2.5 g.of compound of Example 22 and g. of water. A drawdown has a pastel greenvisible color and a strong green luminescence under black light.

EXAMPLE 45 Z-(Z-hydroxyphenyl)-4(3)-quinaz.olone is incorporated at 5%by weight into a polyvinyl chloride homopolymer formulation of 100 partsGeon 103 EP, 2 parts Thermolite 31, and 0.5 part stearic acid. A 2-rollrubber mill is used for incorporation. The mill rolls are gapped at0.010 inch and heated to 165 C. The polymer formulation dry blended withthe 2-(2-hydroxyphenyl)-4(3)-quinazolone is allowed to band and ismilled for 5 minutes. The polymer is again handed and removed from themill as a sheet. Under black light the polymer containing 5% 2-(2-hydroxyphenyl)-4(3J-quinazolone emits a strong green luminescence.

EXAMPLE 46 2 2-hydroxyphenyl -4( 3 -quinazolone is incorporated at 5% byweight into Goodrich Abson ABS polymer using procedure described inExample 45. Under black light the polymer emits a strong greenluminescence.

EXAMPLE 47 2- (Z-hydroxyphenyl) -4 (3 -quinazolone is inco rporated at5% by weight into Hercules Profax 6501 polypropylene using proceduredescribed in Example 45. Under black light polymer emits a strong greenluminescence.

EXAMPLE 48 2-(2-hydroxy-4-ethoxyphenyl)-4(3)-quinazolone is incorporatedinto the PVC homopolymer formulation described in Example 45, using theprocedure of Example 45. The polymer under black light emits a strongblue luminescence.

We claim:

1. A compound of the formula OH R] R] wherein R R and R are eachindividually either hydrogen, hydroxyl, halogen, alkyl of 1-4 carbons oralkoxy of 1-4 carbons, and R is either hydrogen or alkyl of 1-4 carbons.

9. A compound of claim 8 wherein R is hydrogen.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,439,386 4/1948 Guenther et a1 26025l 3,010,9081l/196l Broderick et al 26025l 3,066,105 ll/1962 McCafferty 2602513,127,401 3/1964 Lawes et al 260251 JAMES A. PATTEN, Primary Examiner.

US. Cl. X.R.

260-566; 25230l.2; 240*l.1; 11733.5; 106-2l, 22,288

